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United States PatfifO PREPARATION OF 2,4-BIS(ALKYL)-6-HYDROXY- 1,3,5-TRIAZINES Hansjuergen Schroeder and Christoph J. Grundmann, Columbus, Ohio, assignors to Olin Mathieson Chemical Corporation, a corporation of Virginia No Drawing. Application September 1, 1955 Serial No. 532,120

3 Claims. (Cl. 260-248) Our invention relates to novel 2,4-bis-alkyl substituted)-6-hydroxy-1,3,5-triazines. Our novel compounds have the general formula:

wherein R is an alkyl radical with hydrogen halide, e. g. hydrogen chloride, and an alkali. The alkyl triazine amidine salts are described and claimed in our pending application Serial No. 529,927, filed August22, 1955, and are prepared by catalytic hydrogenolysis of haloalkyl triazine amidines prepared from phosgene and haloalkyl amidines. Treatment of the monohydroxy triazirie amidine salts with hydrogen chloride results in the formation of an amidine hydrochloride and the precipitation of the monohydroxy triazine hydrochloride hydrate. The latter is then converted .to the free hydroxy triazine by treatment with an alkali such as alkaline earth or alkali metal hydroxides, e. g. sodium hydroxide.

The compounds of our invention are useful in preparing 2,4-bis(alkyl)-6-halo-l,3,5-triazines of the general formula:

wherein R is an alkyl radical and X is a halogen, by reaction with a phosphorus oxyhalide. These halo-triazines are described and claimed in our pending application Serial No. 529,928, filed August 22, 1955. They are useful as fungicides and intermediates.

The novel compounds of our invention and their prep aration will be further illustrated by reference to the following example.

2,832,778 Patented Apr. 29, 1958 Example I "liliters of H 0. The solution was cooled to and maintained at 5-10 C. throughout the course of the reaction. A solution of 25 grams of COC1 in 120 milliliters of toluene was added dropwise with eflicient stirring until the pH reached a value of 6. By alternate addition of phosg'erie and more of the above mentioned NaOH solution, the pH was maintained at 8-10. Finally the pH was broii'ght to 6, the precipitated 2,4-bis(trichloromethyl)- 6-hydroxy-1,3,5-triazine-trichloroacetamidine salt was filtered by suction and dried in vacuum over P 0 The yield was 41 grams or 74 percent of theory 'of the salt having a melting point of 2l8-224 C.

Purification for analysis was accomplished by dissolving the product in ethanol and precipitating it with cold water. It then had a melting point of 222224' C.

(B) A mixture of 7.0 grams of the 2,4-bis-(trichl0romethyl)-6-hydroxy-l,3,5-triazine-trichloroacetamidine salt of part A of this example, 13.1 grams of triethylamine, 4 grams of 2 percent palladium on carbon and milliliters of methanol was shaken at room temperature with hydrogen. After the absorption of hydrogen was complete, the catalyst was filtered ofi by suction and a solution of sodium hydroxide was added, to the filtrate, in sufficient amount to convert the triethylamine hydrochloride into triethylamine and sodium chloride. After filtering off the precipitated NaCl, the filtrate was evaporated to dryness at reduced pressure. The residue was taken up with alcohol and the dimethylhydroxytriazine-acetamidine salt was precipitated with ether. The yield was 1.5 grams or 58 percent of the theory of the salt which, after vacuum sublimation, had a melting point of 212-213" C.

O H N Calculated for C7H13N50 3g 5g Fmnd 45194 7100 38:

O H N 01 Calculated for CtH1NaO.HC1.H2O 33. 43 5. 61 23. 40 19. 74 Found 34. 21 6. 41 23. 79 10. 71

(D) A solution comprising 1.17 grams of the 2,4-dimethyl 6 hydroxy 1,3,5 triazine hydrochloride monohydrate in 15 milliliters of methanol was treated with 2.6 milliliters of a 10 percent solution of sodium hydroxide. The methanol was then evaporated in vacuo,

and the residue was sublimed at 158 C. and 0.05 mm. Hg. The sublimate was recrystallized from acetone and the yield was 490 milligrams or 60 percent of the theory of 2,4-dimethyl-6-hydroxy-1,3,5-triazine which melted at 230-231 C.

Calculated for C fiyNsO 47. 99 ,5. 64 33. 57 Found 47. 95 5. 73 33. 52

Example II A mixmre of 0,5 gram of free 2,4-dimethy1-6-hydroxy 1,3,5-triazine, 4 grams of POCl and 0.5 gram of triethylamine was refluxed for 30 minutes. The excess of POCl and the dirnethylchlorotriazine were then removed by distillation. The 2,4-dimethyl-6-chloro-1,3,5-triazine crystallized in the condenser and, after cooling, in the distilled POCl After filtering off from the POCl it was dissolved in ether, filtered, and the ethereal solution evaporated. The residue was recrystallized from Skellysolve.

The yield was 85 milligrams or 15 percent of the theory of product which melted at 64 C.

We claim:

l. A process for preparing 2,4-bis(alkyi)-6-hydroxy- 1,3,5-triazine which comprises reacting 2,4-bis(alkyl)-6- hydroxy-1,3,5-triazine amidine salt of the formula vhydroxy-1,3,5-triazine acetamidine salt with hydrogen .chloride to precipitate 2,4-dimethyl-6-hydroxy-1,3,5-triazine-hydrochloride monohydrate and reacting the hydrochioride monohydrate with sodium hydroxide.

References Cited in the file of this patent UNITED STATES PATENTS 169L018 Joyce Oct. 5, 1954 "2,714,057 Chenicek July 26, 1955 FOREIGN PATENTS 302,011 Italy Oct. 17, 1932 303,047 Italy Nov. 17, 1932 OTHER REFERENCES Beilsteirts Handhuch der Organische Chemie, 4th ed. (1937), vol. 26; page 154, system No. 387-3.

Ostrogovich: Gazz. Chim. Ital., vol. 27 (1897), p. 426- 427.

Adams et al.: J. Org. Chem. 17 No. 8, p. 1163-1164, August 1952. 

1. A PROCESS FOR PREPARING 2,4-BIS(ALKYL)-6-HYDROXY1,3,5-TRIAZINE WHICH COMPRISES REACTING 2,4-BIS(ALKYL)-6HYDROXY-1,3,5-TRIAZINE AMIDINE SALT OF THE FORMULA 